Process for coloring materials



p ea her. in, 193s I j 2,035,518

- 2,035.518- J'ROCESS ron .coLonrNG MATERIALS rritiiior zwiimeyer.cord-ea Hdghts, not, at-

signor to E. 1. du Pont de Nemours & Company, Wilmington, Del.,aeor'poratlonot Delaware No Drawing. Application December 9, 1932,

v SerialNmtiGfiZl This invention relates to processes fordyeing stood byreference to the following illustrative and printing textile fibers andmore particularly examples in which the quantities are stated in toprocesses whereby fibers impregnated parts by weight: with icecolorc'omponents are developed in such Example 1 5 a manner thatshadesof exceptional and heretofore un'obtainable brightness and stability mayA printing paste was prepared according to the UNITED s'rATEs P-ATENToFFicE be obtained. following formula:

It is well. known that insoluble azo dyestuffs 4.8 parts oi thediazo-imino compound of the may be produced on cotton and other textileformula: l material by impregnation with a suitable com- 7 l0 ponentfollowed by treatment with a diaaotized H aromatic amine, neither ofwhich compounds contains a group such as carboxyl or sulfonic acid whichwill render the finished dyestufl. water mwr'iomionion l soluble. Thisexceedingly unsatisfactory method has recently been supplanted by agreatly-improved method whereby adiazo salt is first 0011-1 1 fiifiifizif minfi fifigfig fim i flg obtained by the action of diazotized 450 and/or aikaii This soluble compound mixed methyl'glu' 2o camine 1with a coupling component 14.35 parts of water (160 F.) mm thefibers'The sewn 30 r Turk red oil mud-1s then spl by treatment with suit- Pam WI 5.2 parts of the ortho-toluidide of .2:3 -hy. l hy rolyzing agents.such as acetic acid, at dmxymaphthoic acid elevated temperatures, There-formed diazo salt immediately couples with the ice color coupling5.65 31131; isiltlidium hydroxide solution of component to mrm'msolubledyes or improved 67.0 parts of thickener, made up according to stabilityand m the following formula:

Although this methodof dyeing and printingv 30 is a tremendous advanceover the prior art, 1009 nevertheless, it is subject tomanydisadvantages, 60 parts wheat starch chiefamong which are expensivedevelopment by 580 parts water treatment with steam and acirl vapors;lack of 360 partsgum tragacanth 6% uniformity of the products in manycases; no'-.

" ticeable dullness of the shades; low color eill- 1000 A ciency; andcorrosion of equipment. 0 mm fro an It is an object of the presentinvention to avoid 582; 2 :2 2: fg j 'gf fi paste, then the objectionspreviously enumerated and to prodried It was n treated by immersing f r20 40 duce colors of exceptional brightness. A further seconds'm a bathof thefonowmg composition, 40

* Pmduce a s excenent previously heated to 220 F. and maintained at t0and Washing. A. Ob-

t p tur the develqpinent procject ls'to substitute for theunsatisfactory -devel-' ass: opment process which is at presentpracticed, a

45 new method which is both cheap and convenient. 0 Part glacial aceticacid Additional objects will appear hereinafter. Part strength Theseobjects are attained by the present inparts sodium chloride ventionwherein the impregnated material is M treated with arelatively strongsolution of an b 5o inert salt,; preferably an alkali metal chloride 4such as sodiumchloride, prior to or simultaneous The developed'printedgoods was then rinsed with the hydrolysis ofthe impregnating subwithwater, treated with a hot soapsolution in stances. the usual mannenagainrinsed, then dried. The 55 The invention may be more completelyunderprinted pattern developed as a bright red 55 dyeing. due to theformation of the following in- 5.6 parts of the diazo-imino compound ofthe soluble dyestufl:

CHI

. I N: I A

on l O'ONHQ I 4 5 HI I Ezample z Cotton piece goods was printed as inthe previous example with a printing paste prepared,

according to the following formula;-

l. 5 parts of the diazo-im'ino compound of the probable formula:

probable formula:

4. 0 parts of sodium hydroxide'solution of 30% strength 70.0 parts ofthickener The impregnated fiber wasdeveloped as in the previousexamples, washed, soaped, rinsed and dried. A beautiful yellow dyeingwas obtained due to the formation oi. the dyestufl' of the probablestructure: 7

I (Q-Cl I v (HQ-Cl cnicoonconnpONnooonoocm Ha CH:

obtained by the action of diazotized metaamino-benzo-trifluoride onethyl-xylamine The impregnated fiber was then immersed in thehotconcentrated sodium chloride solution containing acetic and formicacids, as described in the previous example. The developed print was.then washed,scaped, rinsed and dried as before. A brilliant orangepattern was developed,

due'to the-formation of the. dyestuif of the probable structure:

Cotton piece goods was prinie'elwith a printing paste of the followingcomposition:

Example 4 A printing paste was prepared as follows 4.5 parts of thediazo-imino compolmd ab tained by the action of tetrazotized dianisidineon sarcosin, of the probable structure:.

4. 0 parts of the anilide of 2:3-hydroxy-naphthoic acid 3.0 parts ofTurkey red oil 21. 5 parts of water (160 F.)

7. 0 parts 01' sodium hydroxide solution of 30% 1 strength 60.0 partsofthickener Cotton piece goods was printed with the above paste from anengraved roll. The prints were immersed in a cold (50 F.) saturatedsolution of sodium chloride, then exposed to the action of steamcontaining acetic acid vapors. When color development-was completed, thefiber was washed, soaped, rinsed and dried as in the previous examples.The pattern was developed as a bright blue dyeing, due to the formationon the fiber of the dyestufl of the probable structure:

l on. em

on on CONHO com-O Example 5 v Cotton piece goods was impregnated with apaste of the following composition:

. 329 pm; of-the diaso-iiminocompoimd ob 4.0 tained by the actionof'diazotized para- I toluene am --2':'5-dimethoxy-aniline on proline,of'the 3' oat-cm era-Omar. n-uu f on m dron-naphtholcaoid 8.0partsof'mrkey redoil A "21.75partsofwateri160' 1".) 7.0 parts of sodiumhydroxide solution of %strength" 60.0 partsof thickener The'impregnatediiberzwasfthen in the'gfollowing solution, previously cooled to about1.0 part glacialacetic acid 0.5 part formic acid pt 85% strensth 28.0parts sodium chloride 1" 70.5 parts wate 1 Hie "salted and main piecegoods then passed over. a metal-roll heatedto about 220" 1"; suitably bypassing steam through thehollow "can. This treatment results in thedevelopment of a deep blue blaclr dyeing, due. to.the

formation ofthe dyestuif of the probable structure:' I g OCH;

a. oods Wa h d. 0 186, M and in previous examples. mm.- 6 Cotton piecegoods was printed dried with a paste 4.6 parts of the diazo-iminocompound 0btained by the action of diazotized 2:5

diethoxy 4 bentoylamino aniline on nipecotinic-acid, of the probableformula:

. 00am CHs-CHK om-o 1 doom as parts of the ortho-toluidide of2-hydroxy-, anthracene-ii-carboxylic acid 18.1 parts of water (160' F.).4.0 parts ,of sodium hydroxide solution of 30% strength I I 70.0. partsof neutral thickener fiber was dried,then immersed in a coldsalt-acetic-acid-formicdcid solution,

. v 3 fled mm was then subjectedto the action of live steam, resultingin the formation of the green dyestuii. of the probable structurei a, kI 001.com @211 I 4.'=s-m,.m. emulates-,6: 2 :8-hy -i I f rinsedethoxy-4-amino-diphenylamine on bensyl-taurine, of the probablestructure:

2.8 parts of the anilide of 2:3-hydroxynaphthoic acid 3.0 parts ofTurkey red oil 22.5 parts of water (160?) 7.0 parts of sodium hydroxidesolution of 30% strength 60.0 parts of neutral thickener ture , g Aprintingpaste was prepared according to the Example 8 following formula:

4.7 parts of the diazo-imino compound ob- ,tained by the action ofdiazotized alphaamino-anthraquinone onmonoethylortho-toluidihe-para-sulfonic acid, of the probable structure:

-N=NI i I 00 mm as described'in. the previous example; The acidi-.

2.a arts of the a'n'llide of 2:3-hydroxynaphthoic acid 55 parts ofsodium hydroxide solution of 30% strength 3.0 parts of Turkey red oil17.0 parts of water F.) 67.0 parts of thickener stufi produced on thefiber has the probable structure:

00 on co CONE- 3 I Example 9" Cotton piece goods was impregnated with apaste of the following composition:

5.1 parts of the diazo-imino compound 0btained by the action ofdiazotized alphanaphthylamine onmonomethyl-alphanaphthylamine-Z:4-disulfonic acid, of

the probable formula:

3.5 parts' of the anilide of 7-hydroxy-8-carboxy-alpha-naphtho-carbazoleof the probable formula:

17.4 parts water (160 F.)

4.0 parts sodium hydroxide solution of 30% strength 70.0 parts thickenerThe impregnated. fiber was immersed in a saturated solution of potassiumchloride, then subjected to the action of steam containing the vapors offormic acid.. When color. formation was completed, the goods was washed,soaped, rinsed and dried as in previous examples. A uniform black dyeingwas obtained, due to the formation of the dyestufi of' the probableconstitution:

Example 10 Cotton piece goods was printed over its entire surface from aprinting roll with a, paste of the following composition:

3.9 parts of the diazo-imino compound obtained by the action ofdiazotized metanitro-para-toluidine on the omega-sulionic acid" derivedfrom para-toluidine,

of the probable structure:

v 3.1 parts of the orthotoluidide of 2-hydroxycarbazole-3-carboxylicacid 19.0 parts of water (160 F.)

' 4.0 parts of sodium hydroxide solution oi. 30%

strength 70.0 parts of thickener The printed fiber was treated with asalt acid solution, then washed, soaped and dried, as in Examplelyresulting in the dyeing of the fiber with the brown dyestufl of theprobable formula:

I Ha

tions under which this process is carried out may be varied withinrather wide limits without departing from the scope .of the presentinvention. For'instance, as a diazo-imino compound it may be stated ingeneral that compounds having the following formula may be used:

in which an represents an aromatic residue such as a residue of thebenzene, naphthalene, diphenyl, diphenylamine, anthraquinone orcarbazole series free from substituents such as carboxylic or sulfonicacid groups which would render the resulting dyestufl water soluble.-This comr 60- Needless to say the components and condicommon in the icecolor art may be used, .for incooled. and poured into a solution of 18m.of 1 ponent may have substituted'thereon one or more non-watersolubilizin'g radicals, for example alkyl, alkoxy, halogen, nitro,triflurQmethyl, and acylamino groups. It represents a radical resultingfromthe removal of the hydrogen atom attached to the nitrogen of asecondary amineoi the aliphatic, aromatic, or heterocyclic series whichcontains at leastone water'solubilizing group such as carboxylic acid,sulfonic acid, or hydroxyl. V

In general, any of the coupling components stance the arylamides of2:3-hydroxy-naphthoic acid, -hydroxy-carbazol ecarboxylic acids,-hydroxy-naphtho-carbazole carboxylic acids, and

hydroxy-anthracene-carboxylic acids; alphaor beta-naphthol;acylacetyl-derivatives of aromatic amines; alpha-methyl-indole; andaryl-methylpyrazolones.

These mixtures of diazo-imino co'mpoundsand coupling components may thenbe imparted to 'the'flbers in the customary manner, and in con--junction with suitable well-known assistantswhere necessary. Since themanner of-impreghating the fibers with ice colors and the assistantscommonly used thereforare well-known,

enumeration of them is urmecessary and will be omittedfor the s ake ofbrevity.

As is well-known, ice colors may also be produced by a one-bath" methodutilizing mixtures of the arylamides of 2:3-hydroxy-naph thoic acid andnitrosamines, obtained from the bases commonlyused in this art. Such aprocess is described in U. S. Patent 1,121,027, wherein the color isdeveloped on the impregnated fibers byfimmersing in a bichromatesolution. This well-known process may be modifledaccordingto. theprocess of the present invention with excellent results. As anillustration of the means of modifying this "one-bath process Example 1-of the aforementioned patent has been taken and the improvements of thepresent invention incorporated therein: 7

24 Ems. of the anilideof 2:3-hydroxy-naphthoic acid, 40 c. c. of causticsoda lye (35 B.)

and 50 gms. of sodium ricinoleate of 60%,

strength are dissolved in 150 gms. of hot water,

the nitrosamine-alkali metal salt of para-nitraniline of the formula:

, mini metal colored' eflfects to be obtained. a For instance, portionsof the fabric-may be printed with mix--,

tures used in the one-bath" .process and different portions may beprinted with mixtures containing the diazo-imino compounds describedherein, the whole beingsimultaneously developedv according to theprocess of the present invention.-

"The impregnated material may be developed at somewhat elevatedtemperatures, temperatures somewhat above 200 F. being preferred,

although in some cases, depending upon the being developed and otherfactors,

'and mono-chlor-acetic. such as sodium-dihydrogen-phosphate,potaslower'temperatures may be found quite satisfactory. Developmentaccording to the present invention may be carried out by severaldiflerent methods according tothe desires of the manufacturer and theequipment available. For instance, the dyed or printed fiber may beimmersed in a strong solution of the inert salt, and

the material subsequently exposed to steam and acid vapors; immersionmay take place in a hot solution of the inert salt to which has beenadded the acid required for color development; immersion may take placein a cold'solution of the inert salt to which has been added the acidreguired for color development, and thetreated material then exposed tothe action of heat, for exampleby the action of live steam or by passing the impregnated fiber over heated rolls.

The solution of inert salt described herein should contain substantiallynot less than ,partsof salt per hundred parts of solution in the case ofsalts such as sodium chloride which at this concentrationwould produce areasonably strong solution; and should ordinarily be relativelysaturated for optimum results. -It may here be stated that the use ofdilute salt solutionsdoes not permit the advantages of the presentinvention to be achieved, and is expressly from the present invention.Dilute lsalt'solutions are sometimes useful in preventing i'unnlngout"oi the printing composition prior tdcolor development. However, suchsolutions absolutely fail to give the excellent results obtained by theuse of morev concentrated solutions.

are; known to give improved results are alkali metal chlorides, alkalineearth chlorides-alkali .metal sulfates, aluminum sulfate, aluminumchloride, sodium phosphates, zinc chloride and 'zin'c'sulfate. Althoughit may bestated that in general any inert inorganic salt may be used,optimum results appear to be obtained by using a very strong solution ofan alkali metal chloride. It is also possible to use mixtures of two ormore salts.

Where strong solutions" are referred to in the present specification andclaims it is to be' understood that the lower limits of such solutionscorrespond in strength to a 10% solution of sodium chloride. .Theselection of more concentrated solutions, and preferably saturatedsolutlons, isadvisable, as mentioned supra. 111' any event, a solutionwhich is weaker than a 10% sodium chloride solution isnot includedwithin the meaning of theexpression strong solution". For development ofthe colors various acids or acid salts may be used. While the use ofacetic and/or formic acid in their vapor or liquid phase ispreferred,other acids may be substituted therefor among whichare-citric, tartaric, oxalic, In addition acid saltssium-hydrogen-oxalate, and sodium-hydrogensulfate may be substituted forthe customary acetic or formic acids.

', The shades produced by the herein described Among the numerous inertinorganic salts which I processes are considerably brighter than thosepreviously obtained. They are produced bra very simple treatment of theimpregrated .flbers witha material which is both cheap and readilyavailable, andwhich does not require the use of expensive equipment orexceptional. skill. the use of theseprocesses a superior product isproduced at an appreciable saving, consequently they have greatcommercial possibilities.

1 As many apparently widely difierent embodi- 'ments of this inventionmaybe made without dewhich comprises effecting hydrolysis of theimpregnating material in the presence of a substantially saturatedsolution of an inert salt.

2. In the process for the development of ice color printings and dyeingsby subjecting to the action of an acid hydrolyzing agent at elevatedtemperatures fibers impregnated with mixtures of ice color couplingcomponents and derivatives of diazotized aromatic amines which revert tothe diazo salt upon treatment with the hydrolyzing agent, the step whichcomprises efiecting hydrolysis of the impregnating material in thepresence of a substantially saturated solution of an inert salt selectedfrom the group consisting of alkali metal chlorides, alkaline earthchlorides, alkali metal sulfates, aluminum sulfate, aluminum chloride,sodium phosphates, zinc chloride and zinc sulfate.

3. In the-process for the development of ice color printings and dyeingsby subjecting to the action of an acid. hydrolyzing agent at elevatedtemperatures fibers impregnated with mixtures of ice color couplingcomponents'and derivatives of diazotized aromatic amines which revert tothe diazo salt upon treatment with the hydrolyzing agent, the step whichcomprises eflfecting hydrolysis of the impregnating material in thepresence of a strong solution of an alkali metal chloride.

4. In the process for the development of ice color printings and dyeingsby subjecting to the action of an acid hydrolyzing agent at elevatedtemperatures fibers impregnated with mixtures of ice color couplingcomponents and derivatives of diazotized aromatic amines which revert tothe diazo s'alt upon treatment with the hydrolyzing agent, the stepwhich comprises eifecting hydrolysis of the impregnating material in thepresence of a strong solution of sodium chloride.

5. In the process for the development of ice color printings and dyeingsby subjecting to the action of an acid hydrolyzing agent at elevatedtemperatures fibers impregnated with mixtures of ice color couplingcomponents and derivatives of diazotized aromatic amines which revert tothe diazo salt upon treatment with the hydrolyzing agent, the step whichcomprises effecting hydrolysis of the impregnating material in thepresence of a saturated solution of sodium chloride.

6. In the process for the development of ice color printings and dyeingsby subjecting to the action of an acid hydrolyzing agent at elevatedtemperatures fibers impregnated with mixtures of ice color couplingcomponents and water-soluble diazoimino compounds which revert to the 7.In the process for the development of ice I color printings and dyeingsby subjecting to theaction of a dilute acid at elevated temperatures 7fibers impregnated with mixtures of ice color coupling components andwater-soluble diazoimino compounds which revert to the diazo salt upontreatment with the hydrolyzing agent, the step which comprises.eifecting hydrolysis of the impregnating material in the presence of asubstantially saturated solution of an inert salt selected from thegroup consisting of alkali metal chlorides, alkaline earth chlorides,alkali metal sulfates, aluminum sulfate, aluminum chloride, sodiumphosphates, zinc chloride and zinc sulfate.

8. In the process for the development of ice color printings and dyeingsby subjecting to the action of a dilute organic acid at elevatedtemperatures fibers impregnated with mixtures of ice color couplingcomponents and water-soluble diazoimino compounds which revert to thediazo salt upon treatment with the hydrolyzing agent, and have the.following general formula:

in which aryl represents the residue of a diazotized aromatic amine freefrom water-solubilizing groups, and R1 and R2 represent aromatic orallphatic groups or together represent the residue of a heterocyclicimine at least one of which contains at least one water-solubilizinggroup, the step which comprises eifecting hydrolysis 'of theimpregnating material in the presense of a strong solution of an alkalimetal chloride.

9. A solution for the development of ice color printings and dyeingscomprising a hydrolyzing agent capable of converting -derivatives ofdiazotized aromatic amines to their diazo salts, said solution beingsubstantially saturated with an inert salt. 4

10. A solution for the development of ice color printings and dyeingscomprising a hydrolyzing agent capable of converting derivatives ofdiazotized aromatic amines to their diazo salts, said solution beingsubstantially saturated with an inert salt selected from the groupconsisting of alkali metal chlorides, alkaline earth chlorides,alkali-metal sulfates, aluminum sulfate, aluminum chloride, sodiumphosphates, zinc chloride and zinc sulfate.

11. A solution for the development of ice color printings and dyeingscomprising a hydrolyzing tized aromatic amines to their diazo salts,said solution being saturated with sodium chloride.

14. A solution for the development of ice color printings and dyeings.-comprising a dilute acid capable of converting the diazoimino compoundsto their diazo salts, said solution being substantially saturated withan inert salt.

15. The process of claim 8 wherein the ice color coupling component isan arylamide ot .2-3 -hydroxy-naphthoic' acid, R1 and Rs represent all--phatic groups which are components or a single heterocyclic ring, theagent is a member selected from the class consisting of acetic andformic acid and the solution of alkali metal chloride is substantiallysaturated.

16. The process oi claim 8 wherein the ice color coupling component isan arylamide of 2-3-hydroxy-naphthoic acid, the hydrolyzing agent isacetic acid, the developing solution is substantially saturated withsodium chloride and is maintained at temperatures approximating itsboiling point.

17. A solution for the development of ice color printings and dyeingscomprising a dilute organic acid capable of converting to their diazosalts diazoimino compounds having the following general formula:

in which aryl represents the residue 01" a M tizcd aromatic amine treefrom water-solubilizlng groups, and R1 and Ba reprerflnt aromatic oraliphatic groups or together represent the residue of a heterocyc'licimine at least one of which contains at least one water-solubilizinggroup, said solu ltlon being substantially saturated with an inert saltselected from the group consisting oi alkali.

metal chlorides, alkaline earth chlorides, alkali metal sulfates,aluminum sulfate, aluminum chloride, sodium phosphatg, zinc chloride andzinc sulfate.

18. The product of claim 1': wherein R1 and Rs.

represent aliphatic groups which are components of a single heteroyclicring, vthe hydrolyzing agent is a-member oi the class consisting ofacetic and fm'mic acid and the'inert salt is analkali' inert salt is soCERTIFICATE or "commot on.

Patent No. 2,035,518. Maroh 31,1936.

FRITHJOF zwxncmsn.

- .It is hereby certified that error appears i n the printedspecification of the above numbered patent requiring correction asfollows: Page .4, first column, line '40, in the formula,- for thefirst-"H" regd N; page 6, second column, line 34, claim 8, for"presense" read presence; and that-the said sewers Pstentshould be, readwith thesecorrections therein that the same may conform to the record ofthe case in thePatent Office.

Signed and sealed this 26th day of'May, A. D. 1936.

Leslie Frazer (Seal) Acting Commissioner of Patents.

